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I'm looking to find whether water or methanol is more polar, and I'm getting conflicting answers.

My textbook says "the polarity of a bond is quantified by the size of its dipole moment." According to this table, at 20 °C, the dipole moments of methanol and water are 2.87 D and 1.87 D. This implies to me that methanol is more polar.

But there seems to be another measure called "polarity index," which I can't seem to find a definition for online. This table says the polarity indices of methanol and water are 10.2 and 5.1, which implies to me that actually water is more polar.

So what's the difference between the dipole moment and the polarity index? How is the latter defined? And is methanol or water more polar?

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From Roger E. Schirmer "Modern Methods of Pharmaceutical Analysis":

Solvents are generally ranked by polarity, but polarity is not a uniquely defined physical property of a substance. Hence the relative polarity of a solvent will be somewhat dependent on the method used to measure it....

Solvent polarity is a complex function of many parameter in addition to adsorption energy. A more recent ranking of solvents by Snyder is based on a combination of parameter such as dipole moment, proton acceptor or donor properties, and dispersion force solvent...

Snyder's polarity index ranks solvents according to a complex theoretical summation of these properties. As a rule, the higher the polarity index, the more polar the solvent.

Snyder's paper was published in Journal of Chromatography A, Volume 92, Issue 2, 22 May 1974, Pages 223-230 . Take a look at it to see how the index was calculated.

There are different types of polarity indices. And each of them has different parameters and ways to calculate the polarity.

Unlike polarity, dipole moment is a physical property. Polarity indices often take dipole moments as a parameters when calculating the polarity of solvents. The reason why there are polarity indices is because dipole moments alone couldn't explain the nature and interactions of solvents.

Part of your confusion stems from the repetition of the word "polar" to describe different phenomena. There is polarity of bonds and there is polarity of solvents. They are different things.

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  • $\begingroup$ I know bond polarities and molecule polarities are different things, but then what is the dipole moment of an entire molecule measuring? $\endgroup$ – user3932000 Dec 27 '16 at 15:05
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Badyal YS, Saboungi M-L, Price DL, Shastri SD, Haeffner DR, Soper AK. Electron distribution in water. The Journal of Chemical Physics. 2000;112(21):9206-8 gives the dipole moment of water 2.90 +-0.6D, what means that water is more polar then methanol.

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